Process for producing 2,3,3,3-tetrafluoropropene

ABSTRACT

The invention relates to a process to prepare 2-chloro-3,3,3-trifluoropropene (HCO-1233xf) or 2-chloro-1,1,12-tetrafluoropropane (HCFC-244bb) using dichloro-trifluoropropanes and/or trichloro-difluoropropanes, and to prepare 2-chloro-3,3,3-trifluoropropene (HCO-1233xf) using various 242 and 243 isomers.

FIELD OF THE INVENTION

The invention relates to a process to prepare2-chloro-3,3,3-trifluoropropene (HCO-1233xf) or2-chloro-1,1,12-tetrafluoropropane (HCFC-244bb) usingdichloro-trifluoropropanes and/or trichloro-difluoropropanes, and toprepare 2-chloro-3,3,3-trifluoropropene (HCO-1233xf) using various 242and 243 isomers.

BACKGROUND OF THE INVENTION

Certain hydrofluoroolefins (HFOs), such as tetrafluoropropenes(including 2,3,3,3-tetrafluoropropene (HFO-1234yf)), are now known to beeffective refrigerants, heat transfer media, propellants, foamingagents, blowing agents, gaseous dielectrics, sterilant carriers,polymerization media, particulate removal fluids, carrier fluids,buffing abrasive agents, displacement drying agents and power cycleworking fluids. Unlike most chlorofluorocarbons (CFCs) andhydrochlorofluorocarbons (HCFCs), most HFOs pose no threat to the ozonelayer. HFO-1234yf has also been shown to be a low global warmingcompound with low toxicity and, hence, can meet increasingly stringentrequirements for refrigerants in mobile air conditioning. Accordingly,compositions containing HFO-1234yf is a leader among the materials beingdeveloped for use in many of the aforementioned applications.

Several methods of preparing HFOs are known. For example, U.S. Pat. No.4,900,874 (Ihara et al) describes a method of making fluorine containingolefins by contacting hydrogen gas with fluorinated alcohols. Althoughthis appears to be a relatively high-yield process, commercial scalehandling of hydrogen gas at high temperature is potentially hazardous.Also, the cost of commercially producing hydrogen gas, such as buildingan on-site hydrogen plant, is economically costly.

U.S. Pat. No. 2,931,840 (Marquis) describes a method of making fluorinecontaining olefins by pyrolysis of methyl chloride andtetrafluoroethylene or chlorodifluoromethane. This process is arelatively low yield process and a very large percentage of the organicstarting material is converted to unwanted and/or unimportantbyproducts, including a sizeable amount of carbon black which tends todeactivate the catalyst used in the process.

The preparation of HFO-1234yf from trifluoroacetylacetone and sulfurtetrafluoride has been described (See Banks, et al., Journal of FluorineChemistry, Vol. 82, Iss. 2, p. 171-174 (1997)). Also, U.S. Pat. No.5,162,594 (Krespan) discloses a process wherein tetrafluoroethylene isreacted with another fluorinated ethylene in the liquid phase to producea polyfluoroolefin product.

Notwithstanding the above-noted process and other processes forproducing fluorinated olefins in general and fluorinated propenes inparticular, applicants have come to appreciate that a need remains for amore economically efficient means of producing hydrofluoroolefins ingeneral and hydrofluoropropenes in particular, such as HFO-1234yf. Thepresent invention satisfies this need among others.

SUMMARY OF THE INVENTION

It has been found that certain dichlorotrifluoropropane andtrichlorodifluoropropane by-products produced in the manufacture of2-chloro-3,3,3-trifluoropropene (HFO-1233xf) and2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) can be furtherconverted to the desired HFO-1233xf and/or HCFC-244bb product. Suchdichlorotrifluoropropanes include, but are not limited to,2,2-dichloro-1,1,1-trifluoropropane (HCFC-243ab),2,3-dichloro-1,1,1-trifluoropropane (HCFC-243 db),1,2-dichloro-1,1,2-trifluoropropane (HCFC-243bc), and combinationsthereof. Trichlorodifluoropropanes include, but are not limited to,1,2,2-trichloro-1,1-difluoropropane (HCFC-242ac),1,1,2-trichloro-1,2-difluoropropane (HCFC-242bc),1,2,3-trichloro-1,1-difluoropropane (HCFC-242dc), and combinationsthereof.

In one aspect, the present invention relates to a process for preparing2-chloro-3,3,3,-trifluoropropene or 2-chloro-1,1,1,2-tetrafluoropropanethat includes at least the following steps:

-   -   a. providing a feed stream comprising one or more        dichlorotrifluoropropanes, such as        2,2-dichloro-1,1,1-trifluoropropane (HCFC-243ab),        2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db),        1,2-dichloro-1,1,2-trifluoropropane (HCFC-243bc), and        combinations thereof; and/or one or more        trichlorodifluoropropanes such as        1,2,2-trichloro-1,1-difluoropropane (HCFC-242ac),        1,1,2-trichloro-1,2-difluoropropane (HCFC-242bc),        1,2,3-trichloro-1,1-difluoropropane (HCFC-242dc), and        combinations thereof,    -   b. contacting the feed stream with anhydrous hydrogen fluoride        in gas phase in the presence of a fluorination catalyst under        conditions sufficient to produce a product stream comprising        2-chloro-3,3,3,-trifluoropropene and/or        2-chloro-1,1,1,2-tetrafluoropropane, and HCl, and    -   c. isolating 2-chloro-3,3,3,-trifluoropropene and/or        2-chloro-1,1,1,2-tetrafluoropropane from the said product        stream.

In another aspect, the present invention relates to a process forpreparing 2-chloro-3,3,3-trifluoropropene by providing a startingcomposition including at least one compound of formula I, II, and/or III

CX₂═CCl—CH₂X  (I)

CX₃—CCl═CH₂  (II)

CX₃—CHCl—CH₂X  (III)

wherein X is independently selected from F, Cl, Br, and I, provided thatat least one X is not fluorine. Such starting composition is contactedwith a fluorinating agent to produce a final composition including2-chloro-3,3,3-trifluoropropene (1233xf), HCl, unreacted HF, optionalunreacted starting compound(s), and one or more by-products. Theby-products may include one or a combination of trichlorofluoropropene(1231) isomers, 2,3-dichloro-3,3-difluoropropene (1232xf),2-chloro-1,1,1,2-tetrafluoropropane (244bb),1,1,1,2,2-pentafluoropropane (245cb), dichlorotrifluoropropanes (243),trichlorodifluoropropanes (242). The dichlorotrifluoropropanes andtrichlorodifluoropropanes may include, but are not limited to, one or acombination of those compounds identified above or otherwise herein.

This final composition is then processed to separate desired productsand recyclables from the remainder of the composition. In one aspect,1233xf and HCl are first separated by feeding the composition into arecycle or distillation column. From such a column, the lightercomponents, such as 1233xf, 244bb (if any), 245cb (if any), HCl, and aportion of unreacted HF are isolated in a first or top stream, and theremaining organic components, such as unreacted HF, optional unreactedstarted compounds, one or more by-products (e.g. 242 and 243 isomers),and residual 1233xf are recovered in a second or bottom stream. From thetop stream, 1233xf is purified using standard distillation methods, suchas those provided herein. It is then forwarded to the second step of thereaction (discussed below) to produce 244bb and, ultimately, 1234yf.

The bottom stream of the recycle or distillation column is then furtherprocessed to isolate recyclable compounds from the first reaction step.Unreacted HF, for example, is substantially separated by phaseseparation. More specifically, the second or bottom stream from therecycle column is provided to a phase separator where unreacted HFseparates into a first layer. In certain embodiments, this first layeralso includes, as a residual portion, certain of the organics such as,but not limited to, 1233xf, 1232xf, and 243. The remaining organics(e.g. optional unreacted starting compound, residual 1233xf, and one ormore by-products, which may include 1232xf, 242, and/or 243) areseparated into a second layer. The HF-rich first layer is thenextracted, optionally purified, and recycled. The second layer issimilarly extracted and the unreacted starting material (if any) andrecyclable products and/or by-products purified for recycling. Incertain embodiments of the invention, the purified by-productspreferably include at least one or more of the 242 and/or 243 isomersprovided herein which are recycled to the first step fluorinationreaction to produce 1233xf and/or 244bb.

In an alternative embodiment of the foregoing, the final composition ofthe reaction includes each of at least 2-chloro-3,3,3-trifluoropropene(1233xf), HCl, unreacted HF, optional unreacted starting compound,trichlorofluoropropene (1231) isomers, 2,3-dichloro-3,3-difluoropropene(1232xf), a first by-product selected from the group consisting of1,1,1,2-tetrafluoropropane (244bb), 1,1,1,2,2-pentafluoropropane(245cb), and combinations thereof, and a second by-product selected fromthe group consisting of dichlorotrifluoropropane (243),trichlorodifluoropropane (242), and combinations thereof.

The final composition is then fed into a recycle or distillation column,where the lighter components, such as 1233xf, first by-product(s), HCl,and a portion of unreacted HF are isolated from the column in a first ortop stream. The remaining components, such as unreacted HF, optionalunreacted started compounds, residual 1233xf, trichlorofluoropropene(1231) isomers, 2,3-dichloro-3,3-difluoropropene (1232xf), secondby-product(s) and third by-product(s) are recovered in a second orbottom stream.

From the top stream, the 1233xf is purified using standard methods, suchas those described herein, and forwarded to the second stage of thereaction to produce 244bb.

The compounds in the bottom stream may then be further separated toisolate recyclable compounds from the first reaction step. Unreacted HF,for example, is separated by phase separation. More specifically, thesecond stream from the recycle column is provided to a phase separatorwhere the majority of unreacted HF separates into a first layer. Incertain embodiments, this first layer also includes, as a residualportion, certain of the organics such as, but not limited to, 1233xf,1232xf, and 243. The remaining organics not provided in the first layer(e.g. optional unreacted starting compound, residual amounts of 1233xf,1231 isomers, 1232xf, and second and third by-product(s)), and a smallportion of unreacted HF) are separated into a second layer. The firstlayer, which is rich in HF, is then extracted, optionally purified, andrecycled. With the second layer, the optional unreacted startingcompound, trichlorofluoropropene (1231) isomers,2,3-dichloro-3,3-difluoropropene (1232xf), second by-product(s) (e.g.242 and/or 243) are separated from the third by-products by a highboiler purge system and are recycled. The optional unreacted startingcompound, trichlorofluoropropene (1231) isomers,2,3-dichloro-3,3-difluoropropene (1232xf), residual amounts of 1233xfand second by-product(s) may then be recycled to the reactor alone or inconjunction with the second by-products (e.g. 242 and/or 243).

It has been found that the separation of the components in the bottomstream of the first recycle column (e.g. HF, unreacted startingcompound, and certain by-products, such as 242 and 243 isomers) allowsfor easier recycle of reactants back into reactor. The economy of theprocess is also improved by purifying such recycles and removingundesirable by-products that deleteriously affect catalyst life orotherwise degrade the reactor. To this end, the processes of the presentinvention result in reduced catalyst deactivation, as a result of therecycles, and corrosion of the reactor is minimized. The process to thepresent invention also result in higher reaction efficiency andreduction of waste by recycling unreacted and/or underfluorinatedcompounds, which are further converted into the desired products. Tothis end the present invention is further advantageous because itprovides one or more process steps for improving the reaction efficiencyused for the production of HFOs, such as2-chloro-3,3,3,-trifluoropropene (1233xf) or, more broadly, for theproduction of 2,3,3,3-tetrafluoropropene (1234yf), of which 1233xf is aknown intermediate. Additional embodiments and advantages to the presentinvention will be readily apparent to one of skill in the art, based onthe disclosure provided herein.

In another aspect, it has found that in reacting 1233xf with HF to form244bb, varying amounts of 243ab are formed as by-product. This is oftenparticularly the case when a chloride such as HCl is a co-feed to thisreaction. The unwanted generation of 243ab comes at the expense of 244bbyield. In another embodiment of the invention, 243ab formed in thisregard, is converted to 1233xf which can be returned to the reaction toform 244bb. In one practice, the conversion of 243ab to 1233xf is bydehydrochlorination using select catalysts, such as carbon solids, metalhalides, halogenated metal oxides, zero metals, and the like. In apreferred embodiment, the 243ab is dehydrochlorinated in the reactionwhereby 244bb is converted to 1234yf. The 243ab is concurrentlyconverted to 1233xf which can then be re-used as above.

In one embodiment, the invention is to a process to prepare2-chloro-3,3,3-trifluoropropene (HCO-1233xf) or2-chloro-1,1,12-tetrafluoropropane (HCFC-244bb) comprising contacting acompound selected from the group consisting of adichloro-trifluoropropane, a trichloro-difluoropropane, and combinationsthereof, with anhydrous hydrogen fluoride (HF) under conditionseffective to produce 2-chloro-3,3,3-trifluoropropene (HCO-1233xf),2-chloro-1,1,12-tetrafluoropropane (HCFC-244bb), or combinationsthereof. In one embodiment, the process is practiced with the provisothat 2,3-dichloro-1,1,1-trifluoropropane (HCFC-243 db) is excluded fromthe dichloro-trifluoropropanes when preparing HCO-1233xf. In anotherembodiment, the invention is directed to process to prepare2-chloro-1,1,12-tetrafluoropropane (HCFC-244bb) comprising contacting acompound selected from the group consisting of adichloro-trifluoropropane, a trichloro-difluoropropane, and combinationsthereof, with anhydrous hydrogen fluoride (HF) under conditionseffective to produce HCFC-244bb.

In another embodiment, the invention is to a process to prepare2-chloro-3,3,3-trifluoropropene (HCO-1233xf) and2-chloro-1,1,1,2-tetrafluoropropane (244bb) comprising a contacting stepcomprising contacting at least one compound of Formulae (I), (II), (III)

CX₂═CCl—CH₂X  (I)

CX₃—CCl═CH₂  (II)

CX₃—CHCl—CH₂X  (III)

wherein X is independently selected from F, Cl, Br, and I, provided thatat least one X is not fluorine, with anhydrous hydrogen fluoride (HF) inthe presence of a catalyst under conditions effective to form acomposition comprising HCO-1233xf and a by-product selected from thegroup consisting of a dichloro-trifluoropropane, atrichloro-difluoropropane and combinations thereof; recovering theby-product from the composition; recycling the by-product to thecontacting step wherein the by-product is converted to2-chloro-1,1,1,2-tetrafluoropropane (244bb).

In another embodiment, the invention is to a process to prepare2-chloro-3,3,3-trifluoropropene (HCO-1233xf) comprising contacting1,1,1-trifluoro-2,2-dichloropropane (243ab) with a dehydrochlorinationcatalyst under conditions effective to form 1233xf.

DETAILED DESCRIPTION OF THE INVENTION

According to one embodiment, the present invention relates to amanufacturing process for making 2,3,3,3-tetrafluoroprop-1-ene using astarting material according to any one or combination of formulas I, II,and/or III:

CX₂═CCl—CH₂X  (Formula I)

CX₃—CCl═CH₂  (Formula II)

CX₃—CHCl—CH₂X  (Formula III)

wherein X is independently selected from F, Cl, Br, and I, provided thatat least one X is not fluorine. In certain embodiments, the compound(s)of Formula I, II and/or III contains at least one chlorine, a majorityof the Xs as chlorine, or all Xs as chlorine. In certain embodiments,the compound(s) of formula I includes 1,1,2,3-tetrachloropropene(1230xa). In certain embodiments, the compound(s) of formula II includes2,3,3,3-tetrachloropropene (1230xf). In further embodiments, thecompound(s) of formula III include 1,1,1,2,3-pentachloropropane (240db).

The method generally includes at least three reaction steps. In thefirst step, a starting composition including compounds of Formula I, II,and/or III (e.g. 1,1,2,3-tetrachloropropene, 2,3,3,3-tetrachloropropene,and/or 1,1,1,2,3-pentachloropropane) is reacted with anhydrous HF in afirst vapor phase reactor (fluorination reactor) to produce a mixture of2-chloro-3,3,3-trifluoropropene (1233xf) and HCl. In certainembodiments, the reaction occurs in the vapor phase in the presence of avapor phase catalyst, such as, but not limited to, a fluorinatedchromium oxide. The catalyst may (or may not) have to be activated withanhydrous hydrogen fluoride HF (hydrogen fluoride gas) before usedepending on the state of the catalyst.

While fluorinated chromium oxides are disclosed as the vapor phasecatalyst, the present invention is not limited to this embodiment. Anyfluorination catalysts known in the art may be used in this process.Suitable catalysts include, but are not limited to chromium, aluminum,cobalt, manganese, nickel and iron oxides, hydroxides, halides,oxyhalides, inorganic salts thereof and their mixtures and any one ofwhich may be optionally fluorinated. Combinations of catalysts suitablefor the present invention nonexclusively include Cr₂O₃, FeCl₃/C,Cr₂O₃/Al₂O₃, Cr₂O₃/AlF₃, Cr₂O₃/carbon, CoCl₂/Cr₂O₃/Al₂O₃,NiCl₂/Cr₂O₃/Al₂O₃, CoCl₂/AlF₃, NiCl₂/AlF₃ and mixtures thereof. Chromiumoxide/aluminum oxide catalysts are described in U.S. Pat. No. 5,155,082which is incorporated herein by reference. Chromium (III) oxides such ascrystalline chromium oxide or amorphous chromium oxide are preferredwith amorphous chromium oxide being most preferred. Chromium oxide(Cr₂O₃) is a commercially available material which may be purchased in avariety of particle sizes. Fluorination catalysts having a purity of atleast 98% are preferred. The fluorination catalyst is present in anexcess but in at least an amount sufficient to drive the reaction.

This first step of the reaction may be conducted in any reactor suitablefor a vapor phase fluorination reaction. In certain embodiments, thereactor is constructed from materials which are resistant to thecorrosive effects of hydrogen fluoride and catalyst such as Hastalloy,Nickel, Incoloy, Inconel, Monel and fluoropolymer linings. If desired,inert gases such as nitrogen or argon may be employed in the reactorduring operation.

When the compound of formula I is 1230xa, the mol ratio of HF to 1230xain step 1 of the reaction is 1:1 to 50:1, from about 10:1 to about 50:1,or from about 10:1 to about 20:1. The reaction between HF and 1230xa iscarried out at a temperature from about 150° C. to about 500° C., incertain embodiments, about 150° C. to about 400° C., or about 150° C. toabout 300° C. The reaction pressure is about of about 0 psig to about500 psig, in certain embodiments from about 20 psig to about 200 psig,or about 50 to about 100 psig.

Similarly, when the compound of formula II is 1230xf, the mol ratio ofHF to 1230xf in step 1 of the reaction is 1:1 to 50:1, from about 10:1to about 50:1, or from about 10:1 to about 20:1. The reaction between HFand 1230xf is carried out at a temperature from about 150° C. to about500° C., in certain embodiments, about 150° C. to about 400° C., orabout 150° C. to about 300° C. The reaction pressure is about of about 0psig to about 500 psig, in certain embodiments from about 20 psig toabout 200 psig, or about 50 to about 100 psig.

Similarly, when the compound of formula III is 240 db, the mol ratio ofHF to 240 db in step 1 of the reaction is 1:1 to 50:1, from about 10:1to about 50:1, or from about 10:1 to about 20:1. The reaction between HFand 240 db is carried out at a temperature from about 150° C. to about500° C., in certain embodiments, about 150° C. to about 400° C., orabout 150° C. to about 300° C. The reaction pressure is about of about 0psig to about 500 psig, in certain embodiments from about 20 psig toabout 200 psig, or about 50 to about 100 psig.

The fluorination reaction may be carried out to attain a single- ormulti-pass conversion of at least 1% or higher, 5% or higher, 10% orhigher or about 20% or higher. In certain preferred embodiments of thepresent invention, the starting reagent is converted to 1233xf in asingle pass, wherein the reaction conditions achieve a conversion amountgreater than 75%, greater than 85%, greater than 95% or greater than99%. To this end, the resulting effluent includes small or trace amountsof unreacted starting material or may be substantially free of suchcompounds.

The effluent from the fluorination reaction step, including anyintermediate effluents that may be present in multi-stage reactorarrangements, are processed to achieve desired degrees of separationand/or other processing. For example, in embodiments in which thereactor effluent includes 1233xf, the effluent will generally alsoinclude HCl, unreacted HF, and trace amounts, if any, of unreactedstarting component (e.g. 1230xa, 1230xf and/or 240 db). The effluent mayalso include one or more by-product organics such as underfluorinatedand/or overfluorinated intermediates. Non-limiting examples ofunderfluorinated intermediates include trichlorofluoropropene (1231)isomers and 2,3-dichloro-3,3-difluoropropene (1232xf), and non-limitingexamples of overfluorinated intermediates include2-chloro-1,1,1,2-tetrafluoropropane (244bb) and1,1,1,2,2-pentafluoropropane (245cb). Other by-product organics may alsoinclude, but are not limited to, dichlorotrifluoropropane (243), andtrichlorodifluoropropane (242).

In certain embodiments, the reaction by-products include one or more ofdichlorotrifluoropropane and/or trichlorodifluororpropane by-products.Such dichlorotrifluoropropanes include, but are not limited to, one ormore of the compounds 2,2-dichloro-1,1,1-trifluoropropane (HCFC-243ab),2,3-dichloro-1,1,1-trifluoropropane (HCFC-243 db), and1,2-dichloro-1,1,2-trifluoropropane (HCFC-243bc).Trichlorodifluoropropanes include, but are not limited to, one or moreof the compounds 1,2,2-trichloro-1,1-difluoropropane (HCFC-242ac),1,1,2-trichloro-1,2-difluoropropane (HCFC-242bc), and1,2,3-trichloro-1,1-difluoropropane (HCFC-242dc).

The effluent may be processed in one or more steps to isolate the1233xf, as well as certain unreacted components and/or byproducts thatare useful as a recyclables (including, but not limited to, the 242 and243 isomers). Such isolation steps include those known in the art, andinclude without limitation, those described in U.S. Pat. Nos. 8,258,355and 8,084,653 the entire contents of which are incorporated herein byreference. In one embodiment, a first recycle column, such as adistillation column is provided. The lighter components of the effluentare isolated from the top of the first recycle column and cooled andinclude, one or more of HCl, 1233xf, 244bb (if any), 245cb (if any) anda portion of unreacted HF. The remaining compounds are collected at thebottom stream of the column and include a bulk of the unreacted HF,trace amounts of unreacted starting component (if any), residual 1233xfand one or more of the by-product organics discussed herein. Whenreferring to the bottom stream of the column, a “residual” amount of1233xf refers to less than about 30 wt %, less than about 20%, less thanabout 15%, or less than about 10% of the total weight of the componentsin the bottom stream.

Each of the top stream and bottom stream are then independentlyprocessed. The top stream, for example, is first fed into an HCl columnfor HCl removal. High purity HCl is isolated from the top of the columnand fed to an HCl recovery system. By way of non-limiting example, insuch a recovery system HCl from the top stream may be absorbed inde-ionized water as concentrated HCl which, optionally, can be recoveredfor later sale. The remaining components, including 1233xf, 244bb (ifany), 245cb (if any), and HF, exit the bottom of the HCl column and arefurther processed. In certain embodiments, this bottom stream is thenprovided to an HF recovery system to recover HF. The 1233xf/HF stream isfed to a sulfuric acid extractor or a phase separator for removal of HFfrom this mixture, i.e. the HF is either dissolved in sulfuric acid orphase separated from the organic mixture. With the former, HF isdesorbed from the sulfuric acid/HF mixture by heating and distillationand recycled back to the reactor. In the case where a phase separator isused, HF is phase-separated using standard methods, such as thosediscussed below, and recycled back to the reactor. The organic eitherfrom the overhead of the sulfuric acid extractor or from the bottomlayer of the phase separator is fed to the hydrofluorination reactor ofStep (2), discussed below.

Components within the bottom stream of the first recycle column areseparated, in certain embodiments, by phase separation. Morespecifically, the mixture is provided to a cooler and then to a phaseseparator where unreacted HF separates into an HF-rich first or toplayer and an organic rich bottom or second layer. Any pressure whichmaintains the mixture substantially in the liquid phase may be employed.To this end, the pressure and temperature of the mixture may be adjustedsuch that the mixture remains substantially in the liquid phase. Incertain embodiments, the HF-rich layer also includes, as a residualportion, certain of the organics such as, but not limited to 1233xf,1232xf and 243. The remaining organics not provided in the first layer(particularly unreacted starting compound(s) (if any), residual 1233xf,242 isomers, 243 isomers and dimers) separate into the organic-richsecond or bottom layer. (When referring to the top layer, a “residualportion” of organics refers to less than about 50 wt %, less than about40%, less than about 30%, less than about 20%, or less than about 10% ofthe total weight of the components in the top layer.) Phase separationmay be performed at any combination of temperature and pressure suchthat two distinct liquid phases are formed in the phase separator. Phaseseparation may be carried out between about −30° C. to 60° C.,preferably between about 0° C. and 40° C. and more preferably betweenabout 10° C. and 30° C.

The HF rich layer is then isolated, such as by an HF phase pump,optionally purified, and recycled back to the reactor via a vaporizer.In one embodiment, the HF-rich layer is distilled to remove any moisturebuildup or is isolated by single stage flash distillation. In anotherembodiment, before the recycle of HF-rich stream moisture (if any) isremoved by injecting a chemical reagent such as COCl₂ (or SOCl₂) intosaid stream, which reacts with moisture to form CO₂ (or SO₂) and HCl. Ineven further embodiments, the HF-rich layer may be purified to removethe residual organics or may be recycled with the organics.

The organic-rich layer is also isolated, such as by an organic phasepump, then further processed to separate and purify the unreactedstarting reactants (if any) and recyclable intermediates or by-products.In certain embodiments, the organic-rich layer is provided to a highboiler purge system, where unreacted starting reagents (if any),residual 1233xf, 1231 isomers, 1232xf, 243 isomers, 242 isomers, etc.are recovered and undesirable by-products are removed. (When referringto the organic-rich layer, a “residual” amount of HF refers to less thanabout 15 wt %, less than about 10%, less than about 5%, or less thatabout 3% of the total weight of the components in the bottom layer.) Thehigh boiler purge system may be a distillation system operated in batchor continuous mode, preferably batch for operational reasons. Anotheroption is to use a flash or series of flashes. In either case(distillation or flash), the more volatile components are recovered andrecycled while the heavier components are removed from the system.

It has been found that the separation of the components in the bottomstream of the first recycle column into two phases allows for easierrecycle of reactants back into reactor, and that the economy of theprocess is improved by using phase separator followed by purification ofone or both layers before recycling. A presence of moisture in the feed,for example, leads to catalyst deactivation and corrosion of equipmentand piping. Such moisture, if present, will typically concentrate in theHF-rich layer during phase separation. Accordingly, by purifying theHF-rich layer post-isolation, the moisture may be removed and thecatalyst deactivation and corrosion minimized.

Removal of the high boiling point by-products and impurities issimilarly advantageous because such compounds also cause catalystdeactivation if recycled. During phase separation, as set forth above,such compounds tend to concentrate in organic layer. Accordingly,post-isolation, the organic layer can also be purified in accordancewith the foregoing to remove such compounds and isolate only thosecompound that are recyclable. Removal of the high boiling pointcompounds results in improved catalyst life and minimal purge streams.

In the second step of the process for forming2,3,3,3-tetrafluoroprop-1-ene, the purified 1233xf intermediate streamis converted to 2-chloro-1,1,1,2-tetrafluoropropane (244bb). In oneembodiment, this step may be performed in the liquid phase in a liquidphase reactor, which may be TFE or PFA-lined. Such a process may beperformed in a temperature range of about 70-120° C. and about 50-120psig.

Any liquid phase fluorination catalyst may be used in the invention. Anon-exhaustive list include Lewis acids, transition metal halides,transition metal oxides, Group IVb metal halides, Group Vb metalhalides, or combinations thereof. Non-exclusive examples of liquid phasefluorination catalysts are an antimony halide, a tin halide, a tantalumhalide, a titanium halide, a niobium halide, and molybdenum halide, aniron halide, a fluorinated chrome halide, a fluorinated chrome oxide orcombinations thereof. Specific non-exclusive examples of liquid phasefluorination catalysts are SbCl₅, SbCl₃, SbF₅, SnCl₄, TaCl₅, TiCl₄,NbCl₅, MoCl₆, FeCl₃, a fluorinated species of SbCl₅, a fluorinatedspecies of SbCl₃, a fluorinated species of SnCl₄, a fluorinated speciesof TaCl₅, a fluorinated species of TiCl₄, a fluorinated species ofNbCl₅, a fluorinated species of MoCl₆, a fluorinated species of FeCl₃,or combinations thereof. Antimony pentachloride is most preferred.

These catalysts can be readily regenerated by any means known in the artif they become deactivated. One suitable method of regenerating thecatalyst involves flowing a stream of chlorine through the catalyst. Forexample, from about 0.002 to about 0.2 lb per hour of chlorine can beadded to the liquid phase reaction for every pound of liquid phasefluorination catalyst. This may be done, for example, for from about 1to about 2 hours or continuously at a temperature of from about 65° C.to about 100° C.

This second step of the reaction is not necessarily limited to a liquidphase reaction and may also be performed using a vapor phase reaction ora combination of liquid and vapor phases, such as that disclosed in U.S.Published Patent Application No. 20070197842, the contents of which areincorporated herein by reference. To this end, the 1233xf containingfeed stream is preheated to a temperature of from about 50° C. to about400° C., and is contacted with a catalyst and fluorinating agent.Catalysts may include standard vapor phase agents used for such areaction and fluorinating agents may include those generally known inthe art, such as, but not limited to, hydrogen fluoride.

In this second step of the reaction, it is found that 243ab may beformed in varying degrees as a by-product. This is often particularlythe case when a chloride such as HCl is a co-feed to this reaction. Theunwanted generation of 243ab comes at the expense of 244bb yield. In oneaspect of the invention, the 243ab thus formed is converted to 1233xf bycatalytic dehydrochlorination. The 1233xf obtained by this conversioncan be recycled back to the second step of the reaction or used forother purposes. In one embodiment, the 243ab is separately converted torecyclable 1233xf, subject to removal of 243ab from the product mixtureof the second step of the reaction, as known in the art. Preferably, the243ab is sent to the third step of the reaction, discussed hereunder,whereby it is dehydrochlorinated to form 1233xf as part of the processto dehydrochlorinate 244bb to 1234yf. Conveniently, the same reactor,catalysts, and conditions may be employed. The 1233xf thus obtained canbe separated to the extent necessary as known in the art, and can berecycled back to the second step of the reaction whereby 244bb isgenerated, or it can be used otherwise.

In the third step of 1234yf production, the 244bb is fed to a secondvapor phase reactor (dehydrochlorination reactor) to bedehydrochlorinated to make the desired product2,3,3,3-tetrafluoroprop-1-ene (1234yf). This reactor contains a catalystthat can catalytically dehydrochlorinate HCFC-244bb to make HFO-1234yf.

In another aspect of the invention, the 244bb that is fed to the thirdstep of 1234yf production process further comprises all or part of the243ab that may have formed in the second step of the reaction. Thereactor and catalyst suitable for dehydrochlorinating 244bb to 1234yf inthis third step can also act to dehydrochlorinate 243ab to 1233xf, whichcan be optionally reused via recycle.

The catalysts may be metal halides, halogenated metal oxides, neutral(or zero oxidation state) metal or metal alloy, or activated carbon inbulk or supported form. Metal halide or metal oxide catalysts mayinclude, but are not limited to, mono-, bi-, and tri-valent metalhalides, oxides and their mixtures/combinations, and more preferablymono-, and bi-valent metal halides and their mixtures/combinations.Component metals include, but are not limited to, Cr³⁺, Fe³⁺, Mg²⁺,Ca²⁺, Ni²⁺, Zn²⁺, Pd²⁺, Li⁺, Na⁺, K⁺, and Cs⁺. Component halogensinclude, but are not limited to, F⁻, Cl⁻, Br⁻, and I⁻. Examples ofuseful mono- or bi-valent metal halide include, but are not limited to,LiF, NaF, KF, CsF, MgF₂, CaF₂, LiCl, NaCl, KCl, and CsCl. Halogenationtreatments can include any of those known in the prior art, particularlythose that employ HF, F₂, HCl, Cl₂, HBr, Br₂, HI, and I₂ as thehalogenation source.

When neutral, i.e., zero valent, metals, metal alloys and their mixturesare used. Useful metals include, but are not limited to, Pd, Pt, Rh, Fe,Co, Ni, Cu, Mo, Cr, Mn, and combinations of the foregoing as alloys ormixtures. The catalyst may be supported or unsupported. Useful examplesof metal alloys include, but are not limited to, SS 316, Monel 400,Inconel 825, Inconel 600, and Inconel 625. Such catalysts may beprovided as discrete supported or unsupported elements and/or as part ofthe reactor and/or the reactor walls.

Preferred, but non-limiting, catalysts include activated carbon,stainless steel (e.g. SS 316), austenitic nickel-based alloys (e.g.Inconel 625), nickel, fluorinated 10% CsCl/MgO, and 10% CsCl/MgF₂. Thereaction temperature is preferably about 300-550° C. and the reactionpressure may be between about 0-150 psig. The reactor effluent may befed to a caustic scrubber or to a distillation column to remove theby-product of HCl to produce an acid-free organic product which,optionally, may undergo further purification using one or anycombination of purification techniques that are known in the art.

The aforementioned catalysts for dehydrochlorination of 244bb to 1234yfare also useful for dehydrochlorination of 243ab to 1233xf, including inpractices where this latter dehydrochlorination occurs in the third stepof the reaction, as preferred, or is separately performed.

What is claimed is:
 1. A process to prepare2-chloro-1,1,12-tetrafluoropropane (HCFC-244bb) comprising contacting acompound selected from the group consisting of adichloro-trifluoropropane, a trichloro-difluoropropane, and combinationsthereof, with anhydrous hydrogen fluoride (HF) under conditionseffective to produce HCFC-244bb.
 2. The process of claim 1 wherein thedichloro-trifluoropropane is selected from the group consisting of2,2-dichloro-1,1,1-trifluoropropane (HCFC-243ab),1,2-dichloro-1,1,2-trifluoropropane (HCFC-243bc),2,3-dichloro-1,1,1-trifluoropropane (HCFC-243 db) and combinationsthereof.
 3. The process of claim 1 wherein the trichloro-difluoropropaneis selected from the group consisting of1,2,2-trichloro-1,1-difluoropropane (HCFC-242ac),1,1,2-trichloro-1,2-difluoropropane (HCFC-242bc),1,2,3-trichloro-1,1-difluoropropane (HCFC-242dc) and combinationsthereof.
 4. The process of claim 1 wherein the process occurs in a vaporphase.
 5. The process of claim 1 wherein the contacting occurs in thepresence of a catalyst.
 6. The process of claim 5 wherein the catalystis selected from the group consisting of Cr₂O₃, FeCl₃/C, Cr₂O₃/Al₂O₃,Cr₂O₃/AlF₃, Cr₂O₃/carbon, CoCl₂/Cr₂O₃/Al₂O₃, NiCl₂/Cr₂O₃/Al₂O₃,CoCl₂/AlF₃, NiCl₂/AlF₃ and combinations thereof.
 7. The process of claim1 wherein the contacting occurs at a temperature between about 150° C.and about 500° C.
 8. The process of claim 1 wherein the contactingoccurs at a pressure of between about 20 psig and about 200 psig.
 9. Aprocess to prepare 2-chloro-3,3,3-trifluoropropene (HCO-1233xf) and2-chloro-1,1,1,2-tetrafluoropropane (244bb) comprising a contacting stepcomprising contacting at least one compound of Formulae (I), (II), (III)CX₂═CCl—CH₂X  (I)CX₃—CCl═CH₂  (II)CX₃—CHCl—CH₂X  (III) wherein X is independently selected from F, Cl, Br,and I, provided that at least one X is not fluorine, with anhydroushydrogen fluoride (HF) in the presence of a catalyst under conditionseffective to form a composition comprising HCO-1233xf and a by-productselected from the group consisting of a dichloro-trifluoropropane, atrichloro-difluoropropane and combinations thereof; recovering theby-product from the composition; recycling the by-product to thecontacting step wherein the by-product is converted to2-chloro-1,1,1,2-tetrafluoropropane (244bb).
 10. The process of claim 9wherein the recovering step comprises phase separation and distillation.11. The process of claim 9 wherein the catalyst is selected from thegroup consisting of Cr₂O₃, FeCl₃/C, Cr₂O₃/Al₂O₃, Cr₂O₃/AlF₃,Cr₂O₃/carbon, CoCl₂/Cr₂O₃/Al₂O₃, NiCl₂/Cr₂O₃/Al₂O₃, CoCl₂/AlF₃,NiCl₂/AlF₃ and combinations thereof.
 12. The process of claim 9 whereinthe dichloro-trifluoropropane is selected from the group consisting of2,2-dichloro-1,1,1-trifluoropropane (HCFC-243ab),1,2-dichloro-1,1,2-trifluoropropane (HCFC-243bc), and combinationsthereof.
 13. The process of claim 9 wherein thetrichloro-difluoropropane is selected from the group consisting of1,2,2-trichloro-1,1-difluoropropane (HCFC-242ac),1,1,2-trichloro-1,2-difluoropropane (HCFC-242bc), and combinationsthereof.
 14. A process to prepare 2-chloro-3,3,3-trifluoropropene(HCO-1233xf) comprising contacting 1,1,1-trifluoro-2,2-dichloropropane(243ab) with a dehydrochlorination catalyst under conditions effectiveto form 1233xf.
 15. The process of claim 14 wherein thedehydrochlorination catalyst is selected from the group consisting ofcarbon solids, metal halides, halogenated metal oxides, zero metals andcombinations thereof.
 16. A process to prepare2-chloro-1,1,1,2-tetrafluorpropane (244bb) comprising contacting2-chloro-3,3,3-trifluoropropene (HCO-1233xf) with HF in a reaction zoneunder conditions effective to form a composition comprising 244bb and1,1,1-trifluoro-2,2-dichloropropane (243ab); contacting the 243ab with adehydrochlorination catalyst selected from the group consisting ofcarbon solids, metal halides, halogenated metal oxides, zero metals andcombinations thereof under conditions effective to form 1233xf; andrecycling the formed 1233xf to the reaction zone.
 17. A process toprepare 2-chloro-3,3,3-trifluoropropene (HCO-1233xf) comprisingcontacting at least one compound selected from the group consisting of2,2-dichloro-1,1,1-trifluoropropane (HCFC-243ab),1,2-dichloro-1,1,2-trifluoropropane (HCFC-243bc),1,2,2-trichloro-1,1-difluoropropane (HCFC-242ac), and1,2-dichloro-1,1,2-trifluoropropane (HCFC-243bc) in the presence of HFunder conditions effective to form (HCO-1233xf).
 18. The process ofclaim 17 wherein the conditions effective include the presence of acatalyst selected from the group consisting of Cr₂O₃, FeCl₃/C,Cr₂O₃/Al₂O₃, Cr₂O₃/AlF₃, Cr₂O₃/carbon, CoCl₂/Cr₂O₃/Al₂O₃,NiCl₂/Cr₂O₃/Al₂O₃, CoCl₂/AlF₃, NiCl₂/AlF₃ and combinations thereof.